Protease containing dye transfer inhibiting composition

ABSTRACT

A granular detergent composition having a density from 550 to 950 g/liter, said detergent composition comprising 
     i) a polymeric dye transfer inhibiting agent 
     ii) a protease having an isoelectric point below 10 
     iii) a surfactant system which is free of alkylbenzene sulfonate surfactant.

FIELD OF THE INVENTION

The present invention relates to compact granular detergent compositionscontaining a protease having an isoelectric point below 10.

More in particular, the present invention relates to compact granulardye transfer inhibiting compositions comprising a polymeric dye transferinhibiting agent and a protease having an isoelectric point below 10,said compositions further comprising a surfactant system which is freeof alkylbenzene sulfonate.

BACKGROUND OF THE INVENTION

Currently, there is a high interest in "compact" detergent products. Theparticularity of such detergent compositions is their relatively highdensity compared to conventional detergent compositions, and theirability to achieve the same efficiency as conventional detergentcompositions by using a considerably lesser amount of "compact"detergent composition. This particularity is best reflected, in terms ofcomposition, by a relatively low amount of inorganic filler salt. Theefficiency of such "compact" detergent composition is best achieved byeliminating the pre-wash cycle and by using dispersing and diffusingdevices, which are put directly in the drum of the washing machine atthe start of the main washing cycle.

Detergent compositions containing proteases are well-known in art. Byusing a protease in a detergent, it is possible to hydrolyze theproteins, present in stains and soil on the clothes, to such a degreethat they become readily soluble in water.

It is equally well recognized that the relative ability of each proteaseto meet various performance criteria depends at least in part on thecomposition of the detergent matrix. As a consequence, the detergentformulator is faced with a difficult task of providing compact detergentcompositions containing a protease, wherein said protease has anexcellent detergency performance.

The present invention is based on the unexpected finding that in a"compact" matrix containing a polymeric dye transfer inhibiting agentand a non-alkylbenzene sulfonate surfactant system, the detergencyperformance of a protease having an isoelectric point below 10outperforms other proteases having an isoelectric point of higher than10 such as Savinase®, Opticlean®, Maxacal®, Purafect®, and Esperase®.

This finding allows formulation of compact granular detergentcompositions providing both excellent cleaning and fabric careproperties on cotton and woollen fabrics.

According to another embodiment of this invention a process is alsoprovided for laundering operations involving colored fabrics.

SUMMARY OF THE INVENTION

The present invention relates to compact granular detergent compositioncomprising a polymeric dye transfer inhibiting agent and a proteasehaving an isoelectric point below 10, said composition furthercomprising a surfactant system free of alkylbenzene sulfonate.

DETAILED DESCRIPTION OF THE INVENTION

The present detergent compositions are in granular form and arecharacterized by their density, which is higher than the density ofconventional detergent compositions.

The density of the compositions herein ranges from 550 to 950 g/liter,preferably 600 to 900 g/liter of composition, measured at 20° C.

The "compact" form of the compositions herein is best reflected, interms of composition, by the amount of inorganic filler salt; inorganicfiller salts are conventional ingredients of detergent compositions inpowder form; in conventional detergent compositions, the filler saltsare present in substantial amounts, typically 17-35% by weight of thetotal composition.

In the present compositions, the filler salt is present in amounts notexceeding 15% of the total composition, preferably not exceeding 10%,most preferably not exceeding 5% by weight of the composition.

Inorganic filler salts, such as meant in the present compositions areselected from the alkali and alkaline-earth-metal salts of sulphates andchlorides.

A preferred filler salt is sodium sulphate.

Protease

The compact detergent compositions according to the present inventioncomprise a protease having an isoelectric point below 10. Unlikeproteases having an isoelectric point higher than 10, it has been foundthat compact detergent compositions comprising a polymeric dye transferinhibiting agent and a surfactant system free of alkylbenzene sulfonate,when formulated with a protease having an isoelectric point below 10, doprovide both excellent cleaning performance and fabric care performanceon cotton and woollen fabrics.

Suitable proteases include proteases represented by the genus ofSubtilisin Carlsberg, producible by Bacillus licheniformis. Othersuitable proteases include the proteases represented by the genusSubtilisin BPN', producible by Bacillus amyloliquefaciens. Othersuitable proteases are proteases which show a positive immunologicalcross-reaction with the antibody of the proteases as describedhereinabove. Highly preferred proteases are the proteases that arecommercially sold under the tradenames Alcalase®, Maxatase® Optimase®,Primase® or mixtures thereof.

The proteases according to the present invention are present in anamount from 0.001% to 2%, preferably from 0.001% to 1%, more preferablyfrom 0.002% to 0.5% of active enzyme by weight of the detergentcomposition.

Polymeric Dye Transfer Inhibiting Agent

The compact detergent compositions according to the present inventionalso comprise from 0.001% to 10%, preferably from 0.01% to 2%, morepreferably from 0.05% to 1% by weight of a polymeric dye transferinhibiting agents. Said polymeric dye transfer inhibiting agents arenormally incorporated into detergent compositions in order to inhibitthe transfer of dyes from colored fabrics onto fabrics washed therewith.These polymers have the ability to complex or adsorb the fugitive dyeswashed out of dyed fabrics before the dyes have the opportunity tobecome attached to other articles in the wash. Especially suitablepolymeric dye transfer inhibiting agents are polyamine N-oxide polymers,copolymers of N-vinylpyrrolidone and N-vinylimidazole,polyvinylpyrrolidone polymers, polyvinyloxazolidones andpolyvinylimidazoles or mixtures thereof.

a) Polyamine N-oxide polymers

The polyamine N-oxide polymers suitable for use contain units having thefollowing structure formula: ##STR1## wherein P is a polymerisable unit,whereto the R--N--O group can be attached to or wherein the R--N--Ogroup forms part of the polymerisable unit or a combination of both.##STR2## R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclicor alicyclic groups or any combination thereof whereto the nitrogen ofthe N--O group can be attached or wherein the nitrogen of the N--O groupis part of these groups.

The N--O group can be represented by the following general structures:##STR3## wherein R1, R2, and R3 are aliphatic groups, aromatic,heterocyclic or alicyclic groups or combinations thereof, x or/and yor/and z is 0 or 1 and wherein the nitrogen of the N--O group can beattached or wherein the nitrogen of the N--O group forms part of thesegroups.

The N--O group can be part of the polymerisable unit (P) or can beattached to the polymeric backbone or a combination of both.

Suitable polyamine N-oxides wherein the N--O group forms part of thepolymerisable unit comprise polyamine N-oxides wherein R is selectedfrom aliphatic, aromatic, alicyclic or heterocyclic groups.

One class of said polyamine N-oxides comprises the group of polyamineN-oxides wherein the nitrogen of the N--O group forms part of theR-group. Preferred polyamine N-oxides are those wherein R is aheterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine,piperidine, quinoline, acridine and derivatives thereof.

Another class of said polyamine N-oxides comprises the group ofpolyamine N-oxides wherein the nitrogen of the N--O group is attached tothe R-group.

Other suitable polyamine N-oxides are the polyamine oxides whereto theN--O group is attached to the polymerisable unit. Preferred class ofthese polyamine N-oxides are the polyamine N-oxides having the generalformula (I) wherein R is an aromatic, heterocyclic or alicyclic groupswherein the nitrogen of the N--O functional group is part of said Rgroup.

Examples of these classes are polyamine oxides wherein R is aheterocyclic compound such as pyrridine, pyrrole, imidazole andderivatives thereof.

Another preferred class of polyamine N-oxides are the polyamine oxideshaving the general formula (I) wherein R are aromatic, heterocyclic oralicyclic groups wherein the nitrogen of the N--O functional group isattached to said R groups.

Examples of these classes are polyamine oxides wherein R groups can bearomatic such as phenyl.

Any polymer backbone can be used as long as the amine oxide polymerformed is water-soluble and has dye transfer inhibiting properties.Examples of suitable polymeric backbones are polyvinyls, polyalkylenes,polyesters, polyethers, polyamide, polyimides, polyacrylates andmixtures thereof.

The amine N-oxide polymers of the present invention typically have aratio of amine to the amine N-oxide of 10:1 to 1:1000000. However theamount of amine oxide groups present in the polyamine oxide polymer canbe varied by appropriate copolymerization or by appropriate degree ofN-oxidation. Preferably, the ratio of amine to amine N-oxide is from 2:3to 1:1000000. More preferably from 1:4 to 1:1000000, most preferablyfrom 1:7 to 1:1000000. The polymers of the present invention actuallyencompass random or block copolymers where one monomer type is an amineN-oxide and the other monomer type is either an amine N-oxide or not.The amine oxide unit of the polyamine N-oxides has a pKa<10, preferablypKa<7, more preferred pKa<6.

The polyamine oxides can be obtained in almost any degree ofpolymerisation. The degree of polymerisation is not critical providedthe material has the desired water-solubility and dye-suspending power.

Typically, the average molecular weight is within the range of 500 to1000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to30,000, most preferably from 3,000 to 20,000.

b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

The N-vinylimidazole N-vinylpyrrolidone polymers used in the presentinvention have an average molecular weight range from 5,000-1,000,000,preferably from 20,000-200,000.

Highly preferred polymers for use in detergent compositions according tothe present invention comprise a polymer selected from N-vinylimidazoleN-vinylpyrrolidone copolymers wherein said polymer has an averagemolecular weight range from 5,000 to 50,000 more preferably from 8,000to 30,000, most preferably from 10,000 to 20,000.

The average molecular weight range was determined by light scattering asdescribed in Barth H. G. and Mays J. W. Chemical Analysis Vol 113,"Modern Methods of Polymer Characterization".

Highly preferred N-vinylimidazole N-vinylpyrrolidone copolymers have anaverage molecular weight range from 5,000 to 50,000; more preferablyfrom 8,000 to 30,000; most preferably from 10,000 to 20,000.

The N-vinylimidazole N-vinylpyrrolidone copolymers characterized byhaving said average molecular weight range provide excellent dyetransfer inhibiting properties while not adversely affecting thecleaning performance of detergent compositions formulated therewith.

The N-vinylimidazole N-vinylpyrrolidone copolymer of the presentinvention has a molar ratio of N-vinylimidazole to N-vinylpyrrolidonefrom 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, more preferablyfrom 0.6:1 to 0.4:1.

c) Polyvinylpyrrolidone

The detergent compositions of the present invention may also utilizepolyvinylpyrrolidone ("PVP" having an average molecular weight of fromabout 2,500 to about 400,000, preferably from about 5,000 to about200,000, more preferably from about 5,000 to about 50,000, and mostpreferably from about 5,000 to about 15,000. Suitablepolyvinylpyrrolidones are commercially available from ISP Corporation,New York, N.Y. and Montreal, Canada under the product names PVP K-15(viscosity molecular weight of 10,000), PVP K-30 (average molecularweight of 40,000), PVP K-60 (average molecular weight of 160,000), andPVP K-90 (average molecular weight of 360,000). PVP K-15 is alsoavailable from ISP Corporation. Other suitable polyvinylpyrrolidoneswhich are commercially available from BASF Cooperation include SokalanHP 165 and Sokalan HP 12. Polyvinylpyrrolidones known to persons skilledin the detergent field; see for example EP-A-262,897 and EP-A-256,696.

The detergent compositions of the present invention may also utilizepolyvinyloxazolidone as a polymeric dye transfer inhibiting agent. Saidpolyvinyloxazolidones have an average molecular weight of from about2,500 to about 400,000, preferably from about 5,000 to about 200,000,more preferably from about 5,000 to about 50,000, and most preferablyfrom about 5,000 to about 15,000.

The detergent compositions of the present invention may also utilizepolyvinylimidazole as polymeric dye transfer inhibiting agent. Saidpolyvinylimidazoles have an average about 2,500 to about 400,000,preferably from about 5,000 to about 200,000, more preferably, fromabout 5,000 to about 50,000, and most preferably from about 5,000 toabout 15,000.

Surfactant System

The detergent compositions according to the present invention comprise asurfactant system which is free of alkylbenzene sulfonate and whereinthe surfactant can be selected-from nonionic and/or anionic and/orcationic and/or ampholytic and/or zwitterionic and/or semi-polarsurfactants.

Preferred non-alkylbenzene sulfonate surfactant systems to be usedaccording to the present invention comprise as a surfactant one or moreof the nonionic and/or anionic surfactants described herein. Thesesurfactants have found to be very useful in combination with thepolymeric dye transfer inhibiting agents/proteases combination of thethe present invention.

Polyethylene, polypropylene, and polybutylene oxide condensates of alkylphenols are suitable for use as the nonionic surfactant of thesurfactant systems of the present invention, with the polyethylene oxidecondensates being preferred. These compounds include the condensationproducts of alkyl phenols having an alkyl group containing from about 6to about 14 carbon atoms, preferably from about 8 to about 14 carbonatoms, in either a straight-chain or branched-chain configuration withthe alkylene oxide. In a preferred embodiment, the ethylene oxide ispresent in an amount equal to from about 2 to about 25 moles, morepreferably from about 3 to about 15 moles, of ethylene oxide per mole ofalkyl phenol. Commercially available nonionic surfactants of this typeinclude Igepal™ CO-630, marketed by the GAF Corporation; and Triton™X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company.These surfactants are commonly referred to as alkylphenol alkoxylates(e.g., alkyl phenol ethoxylates).

The condensation products of primary and secondary aliphatic alcoholswith from about 1 to about 25 moles of ethylene oxide are suitable foruse as the nonionic surfactant of the nonionic surfactant systems of thepresent invention. The alkyl chain of the aliphatic alcohol can eitherbe straight or branched, primary or secondary, and generally containsfrom about 8 to about 22 carbon atoms. Preferred are the condensationproducts of alcohols having an alkyl group containing from about 8 toabout 20 carbon atoms, more preferably from about 10 to about 18 carbonatoms, with from about 2 to about 10 moles of ethylene oxide per mole ofalcohol. Examples of commercially available nonionic surfactants of thistype include Tergitol™ 15-S-9 (the condensation product of C₁₁ -C₁₅linear alcohol with 9 moles ethylene oxide), Tergitol™ 24-L-6 NMW (thecondensation product of C₁₂ -C₁₄ primary alcohol with 6 moles ethyleneoxide with a narrow molecular weight distribution), both marketed byUnion Carbide Corporation; Neodol™ 45-9 (the condensation product of C₁₄-C₁₅ linear alcohol with 9 moles of ethylene oxide), Neodol™ 23-6.5 (thecondensation product of C₁₂ -C₁₃ linear alcohol with 6.5 moles ofethylene oxide), Neodol™ 45-7 (the condensation product of C₁₄ -C₁₅linear alcohol with 7 moles of ethylene oxide), Neodol™ 45-4 (thecondensation product of C₁₄ -C₁₅ linear alcohol with 4 moles of ethyleneoxide) marketed by Shell Chemical Company, and Kyro™ EOB (thecondensation product of C₁₃ -C₁₅ alcohol with 9 moles ethylene oxide),marketed by The Procter & Gamble Company.

Also useful as the nonionic surfactant of the surfactant systems of thepresent invention are the alkylpolysaccharides disclosed in U.S. Pat.No. 4,565,647, Llenado, issued Jan. 21, 1986, having a hydrophobic groupcontaining from about 6 to about 30 carbon atoms, preferably from about10 to about 16 carbon atoms and a polysaccharide, e.g. a polyglycoside,hydrophilic group containing from about 1.3 to about 10, preferably fromabout 1.3 to about 3, most preferably from about 1.3 to about 2.7saccharide units. Any reducing saccharide containing 5 or 6 carbon atomscan be used, e.g., glucose, galactose and galactosyl moieties can besubstituted for the glucosyl moieties (optionally the hydrophobic groupis attached at the 2-, 3-, 4-, etc. positions thus giving a glucose orgalactose as opposed to a glucoside or galactoside). The intersaccharidebonds can be, e.g., between the one position of the additionalsaccharide units and the 2-, 3-, 4-, and/or 6- positions on thepreceding saccharide units.

The preferred alkylpolyglycosides have the formula

    R.sup.2 O(C.sub.n H.sub.2n O).sub.t (glycosyl).sub.x

wherein R² is selected from the group consisting of alkyl, alkylphenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from about 10 to about 18, preferably from about 12to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 toabout 10, preferably 0; and x is from about 1.3 to about 10, preferablyfrom about 1.3 to about 3, most preferably from about 1.3 to about 2.7.The glycosyl is preferably derived from glucose. To prepare thesecompounds, the alcohol or alkylpolyethoxy alcohol is formed first andthen reacted with glucose, or a source of glucose, to form the glucoside(attachment at the 1-position). The additional glycosyl units can thenbe attached between their 1-position and the preceding glycosyl units2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.

Other suitable nonionic surfactants are the condensation products ofethylene oxide with a hydrophobic base formed by the condensation ofpropylene oxide with propylene glycol. The hydrophobic portion of thesecompounds will preferably have a molecular weight of from about 1500 toabout 1800 and will exhibit water insolubility. The addition ofpolyoxyethylene moieties to this hydrophobic portion tends to increasethe water solubility of the molecule as a whole, and the liquidcharacter of the product is retained up to the point where thepolyoxyethylene content is about 50% of the total weight of thecondensation product, which corresponds to condensation with up to about40 moles of ethylene oxide. Examples of compounds of this type includecertain of the commercially-available Pluronic™ surfactants, marketed byBASF.

Also suitable for use as the nonionic surfactant of the nonionicsurfactant system of the present invention, are the condensationproducts of ethylene oxide with the product resulting from the reactionof propylene oxide and ethylenediamine. The hydrophobic moiety of theseproducts consists of the reaction product of ethylenediamine and excesspropylene oxide, and generally has a molecular weight of from about 2500to about 3000. This hydrophobic moiety is condensed with ethylene oxideto the extent that the condensation product contains from about 40% toabout 80% by weight of polyoxyethylene and has a molecular weight offrom about 5,000 to about 11,000. Examples of this type of nonionicsurfactant include certain of the commercially available Tetronic™compounds, marketed by BASF.

Preferred for use as the nonionic surfactant of the surfactant systemsof the present invention are polyethylene oxide condensates of alkylphenols, condensation products of primary and secondary aliphaticalcohols with from about 1 to about 25 moles of ethylene oxide,alkylpolysaccharides, and mixtures thereof. Most preferred are C₈ -C₁₄alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and C₈ -C₁₈alcohol ethoxylates (preferably C₁₀ avg.) having from 2 to 10 ethoxygroups, and mixtures thereof.

Highly preferred nonionic surfactants are polyhydoxy fatty acid amidesurfactants of the formula. ##STR4## wherein R¹ is H, or R¹ is C₁₋₄hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R²is C₅₋₃₁ hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linearhydrocarbyl chain with at least 3 hydroxyls directly connected to thechain, or an alkoxylated derivative thereof. Preferably, R¹ is methyl,R² is a straight C₁₁₋₁₅ alkyl or alkenyl chain such as coconut alkyl ormixtures thereof, and Z is derived from a reducing sugar such asglucose, fructose, maltose, lactose, in a reductive amination reaction.

When included in such laundry detergent compositions, the nonionicsurfactant systems of the present invention act to improve thegreasy/oily stain removal properties of such laundry detergentcompositions across a broad range of laundry conditions.

Highly preferred anionic surfactants include alkyl alkokylated sulfatesurfactants such as water soluble salts or acids of the formulaRO(A)_(m) SO3M wherein R is an unsubstituted C₁₀ -C₂₄ alkyl orhydroxyalkyl group having a C₁₀ -C₂₄ alkyl component, preferably a C₁₂-C₂₀ alkyl or hydroxyalkyl, more preferably C₁₂ -C₁₈ alkyl orhydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero,typically between about 0.5 and about 6, more preferably between about0.5 and about 3, and M is H or a cation which can be, for example, ametal cation (e. g., sodium, potassium, lithium, calcium, magnesium,etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylatedsulfates as well as alkyl propoxylated sulfates are contemplated herein.Specific examples of substituted ammonium cations include methyl-,dimethyl, trimethyl-ammonium cations and quaternary ammonium cationssuch as tetramethyl-ammonium and dimethyl piperdinium cations and thosederived from alkylamines such as ethylamine, diethylamine,triethylamine, mixtures thereof, and the like. Exemplary surfactants areC₁₂ -C₁₈ alkyl polyethoxylate (1.0) sulfate (C₁₂ -C₁₈ E(1.0)M), C₁₂ -C₁₈alkyl polyethoxylate (2.25) sulfate (C₁₂ -C₁₈ E(2.25)M), C₁₂ -C₁₈ alkylpolyethoxylate (3.0) sulfate (C₁₂ -C₁₈ E(3.0)M), and C₁₂ -C₁₈ alkylpolyethoxylate (4.0) sulfate (C₁₂ -C₁₈ E(4.0)M), wherein M isconveniently selected from sodium and potassium.

Suitable anionic surfactants to be used are alkyl ester sulfonatesurfactants including linear esters of C₈ -C₂₀ carboxylic acids (i.e.,fatty acids) which are sulfonated with gaseous SO₃ according to "TheJournal of the American Oil Chemists Society", 52 (1975), pp. 323-329.Suitable starting materials would include natural fatty substances asderived from tallow, palm oil, etc.

The preferred alkyl ester sulfonate surfactant, especially for laundryapplications, comprise alkyl ester sulfonate surfactants of thestructural formula: ##STR5## wherein R³ is a C₈ -C₂₀ hydrocarbyl,preferably an alkyl, or combination thereof, R⁴ is a C₁ -C₆ hydrocarbyl,preferably an alkyl, or combination thereof, and M is a cation whichforms a water soluble salt with the alkyl ester sulfonate. Suitablesalt-forming cations include metals such as sodium, potassium, andlithium, and substituted or unsubstituted ammonium cations, such asmonoethanolamine, diethanolamine, and triethanolamine. Preferably, R³ isC₁₀ -C₁₆ alkyl, and R⁴ is methyl, ethyl or isopropyl. Especiallypreferred are the methyl ester sulfonates wherein R³ is C₁₀ -C₁₆ alkyl.

Other suitable anionic surfactants include the alkyl sulfate surfactantssuch as water soluble salts or acids of the formula ROSO₃ M wherein Rpreferably is a C₁₀ -C₂₄ hydrocarbyl, preferably an alkyl orhydroxyalkyl having a C₁₀ -C₂₀ alkyl component, more preferably a C₁₂-C₁₈ alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkalimetal cation (e.g. sodium, potassium, lithium), or ammonium orsubstituted ammonium (e.g. methyl-, dimethyl-, and trimethyl ammoniumcations and quaternary ammonium cations such as tetramethyl-ammonium anddimethyl piperdinium cations and quaternary ammonium cations derivedfrom alkylamines such as ethylamine, diethylamine, triethylamine, andmixtures thereof, and the like). Typically, alkyl chains of C₁₂ -C₁₆ arepreferred for lower wash temperatures (e.g. below about 50° C.) andC₁₆₋₁₈ alkyl chains are preferred for higher wash temperatures (e.g.above about 50° C.).

Other anionic surfactants useful for detersive purposes can also beincluded in the laundry detergent compositions of the present invention.These can include salts (including, for example, sodium, potassium,ammonium, and substituted ammonium salts such as mono-, di- andtriethanolamine salts) of soap, C₈ -C₂₂ primary of secondaryalkanesulfonates, C₈ -C₂₄ olefinsulfonates, sulfonated polycarboxylicacids prepared by sulfonation of the pyrolyzed product of alkaline earthmetal citrates, e.g., as described in British patent specification No.1,082,179, C₈ -C₂₄ alkylpolyglycolethersulfates (containing up to 10moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerolsulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxideether sulfates, paraffin sulfonates, alkyl phosphates, isethionates suchas the acyl isethionates, N-acyl taurates, alkyl succinamates andsulfosuccinates, monoesters of sulfosuccinates (especially saturated andunsaturated C₁₂ -C₁₈ monoesters) and diesters of sulfosuccinates(especially saturated and unsaturated C₆ -C₁₂ diesters), acylsarcosinates, sulfates of alkylpolysaccharides such as the sulfates ofalkylpolyglucoside (the nonionic nonsulfated compounds being describedbelow), branched primary alkyl sulfates, and alkyl polyethoxycarboxylates such as those of the formula RO(CH₂ CH₂ O)_(k) --CH₂COO--M+ wherein R is a C₈ -C₂₂ alkyl, k is an integer from 0 to 10, andM is a soluble salt-forming cation. Resin acids and hydrogenated resinacids are also suitable, such as rosin, hydrogenated rosin, and resinacids and hydrogenated resin acids present in or derived from tall oil.

Further examples are described in "Surface Active Agents and Detergents"(Vol. I and II by Schwartz, Perry and Berch). A variety of suchsurfactants are also generally disclosed in U.S. Pat. No.3,929,678,issued Dec. 30, 1975 to Laughlin, et al. at Column 23, line 58 throughColumn 29, line 23 (herein incorporated by reference).

When included therein, the laundry detergent compositions of the presentinvention typically comprise from about 1% to about 40%, preferably fromabout 3% to about 20% by weight of such anionic surfactants.

The laundry detergent compositions of the present invention may alsocontain cationic, ampholytic, zwitterionic, and semi-polar surfactants,as well as the nonionic and/or anionic surfactants other than thosealready described herein. Preferred cationic surfactant systems includenonionic and ampholytic surfactants.

Cationic detersive surfactants suitable for use in the laundry detergentcompositions of the present invention are those having one long-chainhydrocarbyl group. Examples of such cationic surfactants include theammonium surfactants such as alkyldimethylammonium halogenides, andthose surfactants having the formula:

     R.sup.2 (OR.sup.3).sub.y ! R.sup.4 (OR.sup.3).sub.y !.sub.2 R.sup.5 N+X--

wherein R² is an alkyl or alkyl benzyl group having from about 8 toabout 18 carbon atoms in the alkyl chain, each R³ is selected from thegroup consisting of --CH₂ CH₂ --, --CH₂ CH(CH₃)--, --CH₂ CH(CH₂ OH)--,--CH₂ CH₂ CH₂ --, and mixtures thereof; each R⁴ is selected from thegroup consisting of C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl, benzyl ringstructures formed by joining the two R⁴ groups, --CH₂ CHOH--CHOHCOR⁶CHOHCH₂ OH wherein R⁶ is any hexose or hexose polymer having a molecularweight less than about 1000, and hydrogen when y is not 0; R⁵ is thesame as R⁴ or is an alkyl chain wherein the total number of carbon atomsof R² plus R⁵ is not more than about 18; each y is from 0 to about 10and the sum of the y values is from 0 to about 15; and X is anycompatible anion.

Highly preferred cationic surfactants are the water-soluble quaternaryammonium compounds useful in the present composition having the formula:

    R.sub.1 R.sub.2 R.sub.3 R.sub.4 N.sup.+ X.sup.-            (i)

wherein R₁ is C₈ -C₁₆ alkyl, each of R₂, R₃ and R₄ is independently C₁-C₄ alkyl, C₁ -C₄ hydroxy alkyl, benzyl, and --(C₂ H₄)_(x) H where x hasa value from 2 to 5 and X is an anion. Not more than one of R₂, R₃ or R₄should be benzyl.

The preferred alkyl chain length for R₁ is C₁₂ -C₁₅ particularly wherethe alkyl group is a mixture of chain lengths derived from coconut orpalm kernel fat or is derived synthetically by olefin build up or OXOalcohols synthesis.

Preferred groups for R₂ R₃ and R₄ are methyl and hydroxyethyl groups andthe anion X may be selected from halide, methosulphate, acetate andphosphate ions.

Examples of suitable quaternary ammonium compounds of formulae (i) foruse herein are:

coconut trimethyl ammonium chloride or bromide;

coconut methyl dihydroxyethyl ammonium chloride or bromide;

decyl triethyl ammonium chloride;

decyl dimethyl hydroxyethyl ammonium chloride or bromide;

C₁₂₋₁₅ dimethyl hydroxyethyl ammonium chloride or bromide;

coconut dimethyl hydroxyethyl ammonium chloride or bromide;

myristyl trimethyl ammonium methyl sulphate;

lauryl dimethyl benzyl ammonium chloride or bromide;

lauryl dimethyl (ethenoxy)₄ ammonium chloride or bromide;

choline esters (compounds of formula (i) wherein R₁ is --CH₂--O--C--C₁₂₋₁₄ alkyl and R₂ R₃ R₄ are methyl).

O

di-alkyl imidazolines compounds of formula (i)!.

Other cationic surfactants useful herein are also described in U.S. Pat.No. 4,228,044, Cambre, issued Oct. 14, 1980.

When included therein, the laundry detergent compositions of the presentinvention typically comprise from 0% to about 25%, preferably from about3% to about 15% by weight of such cationic surfactants.

Ampholytic surfactants are also suitable for use in the laundrydetergent compositions of the present invention. These surfactants canbe broadly described as aliphatic derivatives of secondary or tertiaryamines, or aliphatic derivatives of heterocyclic secondary and tertiaryamines in which the aliphatic radical can be straight- orbranched-chain. One of the aliphatic substituents contains at leastabout 8 carbon atoms, typically from about 8 to about 18 carbon atoms,and at least one contains an anionic water-solubilizing group, e.g.carboxy, sulfonate, sulfate. See U.S. Pat. No. 3,929,678 to Laughlin etal., issued Dec. 30, 1975 at column 19, lines 18-35, for examples ofampholytic surfactants.

When included therein, the laundry detergent compositions of the presentinvention typically comprise from 0% to about 15%, preferably from about1% to about 10% by weight of such ampholytic surfactants.

Zwitterionic surfactants are also suitable for use in laundry detergentcompositions. These surfactants can be broadly described as derivativesof secondary and tertiary amines, derivatives of heterocyclic secondaryand tertiary amines, or derivatives of quaternary ammonium, quaternaryphosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678to Laughlin et al., issued Dec. 30, 1975 at column 19, line 38 throughcolumn 22, line 48, for examples of zwitterionic surfactants.

When included therein, the laundry detergent compositions of the presentinvention typically comprise from 0% to about 15%, preferably from about1% to about 10% by weight of such zwitterionic surfactants.

Semi-polar nonionic surfactants are a special category of nonionicsurfactants which include water-soluble amine oxides containing onealkyl moiety of from about 10 to about 18 carbon atoms and 2 moietiesselected from the group consisting of alkyl groups and hydroxyalkylgroups containing from about 1 to about 3 carbon atoms; water-solublephosphine oxides containing one alkyl moiety of from about 10 to about18 carbon atoms and 2 moieties selected from the group consisting ofalkyl groups and hydroxyalkyl groups containing from about 1 to about 3carbon atoms; and water-soluble sulfoxides containing one alkyl moietyof from about 10 to about 18 carbon atoms and a moiety selected from thegroup consisting of alkyl and hydroxyalkyl moieties of from about 1 toabout 3 carbon atoms.

Semi-polar nonionic detergent surfactants include the amine oxidesurfactants having the formula ##STR6## wherein R³ is an alkyl,hydroxyalkyl, or alkyl phenyl group or mixtures therof containing fromabout 8 to about 22 carbon atoms; R⁴ is an alkylene or hydroxyalkylenegroup containing from about 2 to about 3 carbon atoms or mixturesthereof; x is from 0 to about 3; and each R⁵ is an alkyl or hydroxyalkylgroup containing from about 1 to about 3 carbon atoms or a polyethyleneoxide group containing from about 1 to about 3 ethylene oxide groups.The R⁵ groups can be attached to each other, e.g., through an oxygen ornitrogen atom, to form a ring structure.

These amine oxide surfactants in particular include C₁₀ -C₁₈ alkyldimethyl amine oxides and C₈ -C₁₂ alkoxy ethyl dihydroxy ethyl amineoxides.

When included therein, the laundry detergent compositions of the presentinvention typically comprise from 0% to about 15%, preferably from about1% to about 10% by weight of such semi-polar nonionic surfactants.

The present invention further provides laundry detergent compositionscomprising at least 1% by weight, preferably from about 3% to about 65%,more preferably from about 10% to about 25% by weight of totalsurfactants.

Optional Detergent Ingredients

Preferred detergent compositions of the present invention may furthercomprise an enzyme which provide fabric care benefits. Said enzymesinclude enzymes selected from cellulases, peroxidases or mixturesthereof.

The cellulases usable in the present invention include both bacterial orfungal cellulase. Preferably, they will have a pH optimum of between 5and 9.5. Suitable cellulases are disclosed in U.S. Pat. No. 4,435,307,Barbesgoard et al, which discloses fungal cellulase produced fromHumicola insolens. Suitable cellulases are also disclosed inGB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.

Examples of such cellulases are cellulases produced by a strain ofHumicola insolens (Humicola grisea var. thermoidea), particularly theHumicola strain DSM 1800.

Other suitable cellulases are cellulases originated from Humicolainsolens having a molecular weight of about 50 KDa, an isoelectric pointof 5.5 and containing 415 amino acids. Such cellulase are described inCopending European patent application No. 93200811.3, filed Mar. 19,1993. Especially suitable cellulase are the cellulase having color carebenefits. Examples of such cellulases are cellulase described inEuropean patent application No. 91202879.2, filed Nov. 6, 1991 Carezyme(Novo).

Peroxidase enzymes are used in combination with oxygen sources, e.g.percarbonate, perborate, persulfate, hydrogen peroxide, etc. They areused for "solution bleaching", i.e. to prevent transfer of dyes ofpigments removed from substrates during wash operations to othersubstrates in the wash solution. Peroxidase enzymes are known in theart, and include, for example, horseradish peroxidase, ligninase, andhaloperoxidase such as chloro- and bromo-peroxidase.Peroxidase-containing detergent compositions are disclosed, for example,in PCT International Application WO 89/099813 and in European Patentapplication EP No. 91202882.6, filed on Nov. 6, 1991.

Said cellulases and/or peroxidases are normally incorporated in thedetergent composition at levels from 0.0001% to 2% of active enzyme byweight of the detergent composition.

Other preferred enzymes that can be included in the detergentcompositions of the present invention include lipases. Suitable lipaseenzymes for detergent usage include those produced by microorganisms ofthe Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, asdisclosed in British Patent 1,372,034. Suitable lipases include thosewhich show a positive immunological cross-reaction with the antibody ofthe lipase, produced by the microorganism Pseudomonas fluorescent IAM1057. This lipase is available from Amano Pharmaceutical Co. Ltd.,Nagoya, Japan, under the trade name Lipase P "Amano," hereinafterreferred to as "Amano-P". Especially suitable lipases are lipases suchas M1 Lipase (Gist-Brocades) and Lipolase (Novo) which have found to bevery effective when used in combination with the compositions of thepresent invention.

The lipases are normally incorporated in the detergent composition atlevels from 0.0001% to 2% of active enzyme by weight of the detergentcomposition.

Other detergent ingredients that can be included are detersive enzymeswhich can be included in the detergent formulations for a wide varietyof purposes. Amylases can be included for removal of carbohydrate-basedstains.

Other types of enzymes e.g oxidases, reductases may also be included.They may be of any suitable origin, such as vegetable, animal,bacterial, fungal and yeast origin.

Said enzymes are normally incorporated in the detergent composition atlevels from 0.0001% to 2% of active enzyme by weight of the detergentcomposition.

Other suitable detergent ingredients that can be added are enzymeoxidation scavengers which are described in Copending European Patentaplication N 92870018.6 filed on Jan. 31, 1992. Examples of such enzymeoxidation scavengers are ethoxylated tetraethylene polyamines.

Especially preferred detergent ingredients are combinations withtechnologies which also provide a type of color care benefit. Examplesof these technologies are metallo catalysts for color maintenance. Suchmetallo catalysts are described in copending European Patent ApplicationNo. 92870181.2.

Additional detergent ingredients that can be included in the detergentcompositions of the present invention include bleaching agents. Thesebleaching agent components can include one or more oxygen bleachingagents and, depending upon the bleaching agent chosen, one or morebleach activators. When present bleaching compounds will typically bepresent at levels of from about 1% to about 10%, of the detergentcomposition. In general, bleaching compounds are optional components innon-liquid formulations, e.g. granular detergents. If present, theamount of bleach activators will typically be from about 0.1% to about60%, more typically from about 0.5% to about 40% of the bleachingcomposition.

The bleaching agent component for use herein can be any of the bleachingagents useful for detergent compositions including oxygen bleaches aswell as others known in the art.

The bleaching agent suitable for the present invention can be anactivated or non-activated bleaching agent.

One category of oxygen bleaching agent that can be used encompassespercarboxylic acid bleaching agents and salts thereof. Suitable examplesof this class of agents include magnesium monoperoxyphthalatehexahydrate, the magnesium salt of meta-chloro perbenzoic acid,4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.Such bleaching agents are disclosed in U.S. Pat. No. 4,483,781, U.S.patent application Ser. No. 740,446, European Patent Application0,133,354 and U.S. Pat. No. 4,412,934. Highly preferred bleaching agentsalso include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S.Pat. No. 4,634,551.

Another category of bleaching agents that can be used encompasses thehalogen bleaching agents. Examples of hypohalite bleaching agents, forexample, include trichloro isocyanuric acid and the sodium and potassiumdichloroisocyanurates and N-chloro and N-bromo alkane sulphonamides.Such materials are normally added at 0.5-10% by weight of the finishedproduct, preferably 1-5% by weight.

The hydrogen peroxide releasing agents can be used in combination withbleach activators such as tetraacetylethylenediamine (TAED),nonanoyloxybenzene-sulfonate (NOBS, described in U.S. Pat. No.4,412,934), 3,5,-trimethylhexanoloxybenzenesulfonate (ISONOBS, describedin EP 120,591) or pentaacetylglucose (PAG), which are perhydrolyzed toform a peracid as the active bleaching species, leading to improvedbleaching effect. Also suitable activators are acylated citrate esterssuch as disclosed in Copending European Patent Application No.91870207.7.

The hydrogen peroxide may also be present by adding an enzymatic system(i.e. an enzyme and a substrate therefore) which is capable ofgenerating hydrogen peroxide at the beginning or during the washingand/or rinsing process. Such enzymatic systems are disclosed in EPPatent Application 91202655.6 filed Oct. 9, 1991.

Other peroxygen bleaches suitable for the present invention includeorganic peroxyacids such as percarboxylic acids.

Bleaching agents other than oxygen bleaching agents are also known inthe art and can be utilized herein. One type of non-oxygen bleachingagent of particular interest includes photoactivated bleaching agentssuch as the sulfonated zinc and/or aluminum phthalocyanines. Thesematerials can be deposited upon the substrate during the washingprocess. Upon irradiation with light, in the presence of oxygen, such asby hanging clothes out to dry in the daylight, the sulfonated zincphthalocyanine is activated and, consequently, the substrate isbleached. Preferred zinc phthalocyanine and a photoactivated bleachingprocess are described in U.S. Pat. No. 4,033,718. Typically, detergentcompositions will contain about 0.025% to about 1.25%, by weight, ofsulfonated zinc phthalocyanine.

The compositions according to the present invention may further comprisea builder system. Any conventional builder system is suitable for useherein including aluminosilicate materials, silicates, polycarboxylatesand fatty acids, materials such as ethylenediamine tetraacetate, metalion sequestrants such as aminopolyphosphonates, particularlyethylenediamine tetramethylene phosphonic acid and diethylene triaminepentamethylenephosphonic acid. Though less preferred for obviousenvironmental reasons, phosphate builders can also be used herein.

Suitable builders can be an inorganic ion exchange material, commonly aninorganic hydrated aluminosilicate material, more particularly ahydrated synthetic zeolite such as hydrated zeolite A, X, B or HS.

Another suitable inorganic builder material is layered silicate, e.g.SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting ofsodium silicate (Na₂ Si₂ O₅).

Suitable polycarboxylates containing one carboxy group include lacticacid, glycolic acid and ether derivatives thereof as disclosed inBelgian Patent Nos. 831,368, 821,369 and 821,370. Polycarboxylatescontaining two carboxy groups include the water-soluble salts ofsuccinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid,diglycollic acid, tartaric acid, tartronic acid and fumaric acid, aswell as the ether carboxylates described in German Offenlegenschrift2,446,686, and 2,446,687 and U.S. Pat. No. 3,935,257 and the sulfinylcarboxylates described in Belgian Patent No. 840,623. Polycarboxylatescontaining three carboxy groups include, in particular, water-solublecitrates, aconitrates and citraconates as well as succinate derivativessuch as the carboxymethyloxysuccinates described in British Patent No.1,379,241, lactoxysuccinates described in Netherlands Application7205873, and the oxypolycarboxylate materials such as2-oxa-1,1,3-propane tricarboxylates described in British Patent No.1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinatesdisclosed in British Patent No. 1,261,829, 1,1,2,2-ethanetetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propanetetracarboxylates. Polycarboxylates containing sulfo substituentsinclude the sulfosuccinate derivatives disclosed in British Patent Nos.1,398,421 and 1,398,422 and in U.S. Pat. No. 3,936,448, and thesulfonated pyrolysed citrates described in British Patent No. 1,082,179,while polycarboxylates containing phosphone substituents are disclosedin British Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates includecyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienidepentacarboxylates,2,3,4,5-tetrahydro-furan-cis,cis,cis-tetracarboxylates,2,5-tetrahydro-furan-cis-dicarboxylates,2,2,5,5-tetrahydrofuran-tetracarboxylates,1,2,3,4,5,6-hexane-hexacarboxylates and and carboxymethyl derivatives ofpolyhydric alcohols such as sorbitol, mannitol and xylitol. Aromaticpoly-carboxylates include mellitic acid, pyromellitic acid and thephthalic acid derivatives disclosed in British Patent No. 1,425,343.

Of the above, the preferred polycarboxylates are hydroxycarboxylatescontaining up to three carboxy groups per molecule, more particularlycitrates.

Preferred builder systems for use in the present compositions include amixture of a water-insoluble aluminosilicate builder such as zeolite Aor of a layered silicate (SKS-6), and a water-soluble carboxylatechelating agent such as citric acid.

A suitable chelant for inclusion in the detergent compositions inaccordance with the invention is ethylenediamine-N,N'-disuccinic acid(EDDS) or the alkali metal, alkaline earth metal, ammonium, orsubstituted ammonium salts thereof, or mixtures thereof. Preferred EDDScompounds are the free acid form and the sodium or magnesium saltthereof. Examples of such preferred sodium salts of EDDS include Na₂EDDS and Na₄ EDDS. Examples of such preferred magnesium salts of EDDSinclude MgEDDS and Mg₂ EDDS. The magnesium salts are the most preferredfor inclusion in compositions in accordance with the invention.

Preferred builder systems include a mixture of a water-insolublealuminosilicate builder such as zeolite A, and a watersolublecarboxylate chelating agent such as citric acid. Other builder materialsthat can form part of the builder system for use in granularcompositions include inorganic materials such as alkali metalcarbonates, bicarbonates, silicates, and organic materials such as theorganic phosphonates, amino polyalkylene phosphonates and aminopolycarboxylates.

Other suitable water-soluble organic salts are the homo- or co-polymericacids or their salts, in which the polycarboxylic acid comprises atleast two carboxyl radicals separated from each other by not more thantwo carbon atoms. Polymers of this type are disclosed in GB-A-1,596,756.Examples of such salts are polyacrylates of MW 2000-5000 and theircopolymers with maleic anhydride, such copolymers having a molecularweight of from 20,000 to 70,000, especially about 40,000.

Detergency builder salts are normally included in amounts of from 10% to80% by weight of the composition preferably from 20% to 70% and mostusually from 30% to 60% by weight.

Another optional ingredient is a suds suppressor, exemplified bysilicones, and silica-silicone mixtures. Silicones can be generallyrepresented by alkylated polysiloxane materials while silica is normallyused in finely divided forms exemplified by silica aerogels and xerogelsand hydrophobic silicas of various types. These materials can beincorporated as particulates in which the suds suppressor isadvantageously releasably incorporated in a water-soluble orwater-dispersible, substantially non-surface-active detergentimpermeable carrier. Alternatively the suds suppressor can be dissolvedor dispersed in a liquid carrier and applied by spraying on to one ormore of the other components.

A preferred silicone suds controlling agent is disclosed in Bartollotaet al. U.S. Pat. No. 3,933,672. Other particularly useful sudssuppressors are the self-emulsifying silicone suds suppressors,described in German Patent Application DTOS 2 646 126 published Apr. 28,1977. An example of such a compound is DC-544, commercially availablefrom Dow Corning, which is a siloxane-glycol copolymer. Especiallypreferred suds controlling agent are the suds suppressor systemcomprising a mixture of silicone oils and 2-alkyl-alcanols. Suitable2-alkyl-alkanols are 2-butyl-octanol which are commercially availableunder the trade name Isofol 12 R. Such suds suppressor system aredescribed in Copending European Patent application N 92870174.7 filed 10Nov., 1992.

Especially preferred silicone suds controlling agents are described inCopending European Patent application N°92201649.8. Said compositionscan comprise a silicone/silica mixture in combination with fumednonporous silica such as Aerosil®.

The suds suppressors described above are normally employed at levels offrom 0.001% to 2% by weight of the composition, preferably from 0.01% to1% by weight.

Other components used in detergent compositions may be employed, such assoil-suspending, agents soil-release agents, optical brighteners,abrasives, bactericides, tarnish inhibitors, coloring agents, and/orencapsulated or non-encapsulated perfumes.

Especially suitable encapsulating materials are water soluble capsuleswhich consist of a matrix of polysaccharide and polyhydroxy compoundssuch as described in GB 1,464,616.

Other suitable water soluble encapsulating materials comprise dextrinsderived from ungelatinized starch acid-esters of substituteddicarboxylic acids such as described in U.S. Pat. No. 3,455,838. Theseacid-ester dextrins are, preferably, prepared from such starches as waxymaize, waxy sorghum, sago, tapioca and potato. Suitable examples of saidencapsulating materials include N-Lok manufactured by National Starch.The N-Lok encapsulating material consisits of a modified maize starchand glucose. The starch is modified by adding monofunctional substitutedgroups such as octenyl succinic acid anhydride.

Other suitable detergent ingredients that can be added to thecompositions of the present invention include fabric softening clayssuch as described in European Patent application No. 522 206.

Antiredeposition and soil suspension agents suitable herein includecellulose derivatives such as methylcellulose, carboxymethylcelluloseand hydroxyethylcellulose, and homo- or co-polymeric polycarboxylicacids or their salts. Polymers of this type include the polyacrylatesand maleic anhydride-acrylic acid copolymers previously mentioned asbuilders, as well as copolymers of maleic anhydride with ethylene,methylvinyl ether or methacrylic acid, the maleic anhydride constitutingat least 20 mole percent of the copolymer. These materials are normallyused at levels of from 0.5% to 10% by weight, more preferably from 0.75%to 8%, most preferably from 1% to 6% by weight of the composition.

Preferred optical brighteners are anionic in character, examples ofwhich are disodium4,4'-bis-(2-diethanolamino-4-anilino-s-triazin-6-ylamino)stilbene-2:2'disulphonate, disodium4,-4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylaminostilbene-2:2'-disulphonate,disodium4,4'-bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2'-disulphonate,monosodium4',4"-bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2-sulphonate,disodium4,4'-bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2'-disulphonate,disodium4,4'-bis-(4-phenyl-2,1,3-triazol-2-yl)-stilbene-2,2'disulphonate,disodium4,4'bis(2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2'disulphonateand sodium2(stilbyl-4"-(naphtho-1',2':4,5)-1,2,3-triazole-2"-sulphonate.

Other useful polymeric materials are the polyethylene glycols,particularly those of molecular weight 1000-10000, more particularly2000 to 8000 and most preferably about 4000. These are used at levels offrom 0.20% to 5% more preferably from 0.25% to 2.5% by weight. Thesepolymers and the previously mentioned homo- or co-polymericpolycarboxylate salts are valuable for improving whiteness maintenance,fabric ash deposition, and cleaning performance on clay, proteinaceousand oxidizable soils in the presence of transition metal impurities.

Soil release agents useful in compositions of the present invention areconventionally copolymers or terpolymers of terephthalic acid withethylene glycol and/or propylene glycol units in various arrangements.Examples of such polymers are disclosed in the commonly assigned U.S.Pat. Nos. 4,116,885 and 4,711,730 and European Published PatentApplication No. 0 272 033. A particular preferred polymer in accordancewith EP-A-0 272 033 has the formula

    (CH.sub.3 (PEG).sub.43).sub.0.75 (POH).sub.0.25  T--PO).sub.2.8 (T--PEG).sub.0.4 !T(PO--H).sub.0.25 ((PEG).sub.43 CH.sub.3).sub.0.75

where PEG is --(OC₂ H₄)O--, PO is (OC₃ H₆ O) and T is (pcOC₆ H₄ CO).

Also very useful are modified polyesters as random copolymers ofdimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and1-2 propane diol, the end groups consisting primarily of sulphobenzoateand secondarily of mono esters of ethylene glycol and/or propane-diol.The target is to obtain a polymer capped at both end by sulphobenzoategroups, "primarily", in the present context most of said copolymersherein will be end-capped by sulphobenzoate groups. However, somecopolymers will be less than fully capped, and therefore their endgroups may consist of monoester of ethylene glycol and/or propane 1-2diol, thereof consist "secondarily" of such species.

The selected polyesters herein contain about 46% by weight of dimethylterephthalic acid, about 16% by weight of propane -1.2 diol, about 10%by weight ethylene glycol about 13% by weight of dimethyl sulfobenzoicacid and about 15% by weight of sulfoisophthalic acid, and have amolecular weight of about 3.000. The polyesters and their method ofpreparation are described in detail in EPA 311 342.

The present invention also relates to a process for inhibiting dyetransfer from one fabric to another of solubilized and suspended dyesencountered during fabric laundering operations involving coloredfabrics.

The process comprises contacting fabrics with a laundering solution ashereinbefore described.

The process of the invention is conveniently carried out in the courseof the washing process. The washing process is preferably carried out at5° C. to 95° C., especially 20 to 60, but the polymers are effective atup to 95° C. and higher temperatures. The pH of the treatment solutionis preferably from 7 to 11, especially from 7.5 to 10.5.

The process and compositions of the invention can also be used asdetergent additive products.

Such additive products are intended to supplement or boost theperformance of conventional detergent compositions.

The detergent compositions according to the present invention includecompositions which are to be used for cleaning substrates, such asfabrics, fibers, hard surfaces, skin etc., for example hard surfacecleaning compositions (with or without abrasives), laundry detergentcompositions, automatic and non automatic dishwashing compositions.

The following examples are meant to exemplify compositions of thepresent invention, but are not necessarily meant to limit or otherwisedefine the scope of the invention, said scope being determined accordingto claims which follow.

EXAMPLE I (A/B/C/D/E)

    ______________________________________    % by weight of the total detergent composition                    A    B      C      D    E    ______________________________________    Polyhydroxy fatty acid amide                      --     --     --   --   --    Alkyl alkoxylated sulfate                      1      2.0    2.0  2.5  --    Alkyl sulphate    9      8.0    8.0  8.5  19    C.sub.45 alcohol 7 times ethoxylate                      8      4.5    10.0 4.5  2.0    Tallow alcohol 11 times                      --     --     --   1.5  1.8    ethoxylated    Coconut dimethyl hydroxy                      --     2.0    --   --   0.07    ethyl ammonium chloride    Dispersant        0.07   0.07   0.07 0.07 0.07    Silicone fluid    0.80   0.80   0.80 0.80 0.8    Trisodium citrate 10.0   5.0    5.0  10.0 --    Citric acid       --     4.0    4.0  --   --    Na Carbonate/Na bicarbonate                      17.5   18.0   18.0 21.0 --    Zeolite           26.0   15.0   21.0 35   52    SKS-6             --     9.0    12.5 --   --    Diethylenetriamine pentan-                      0.8    0.4    0.4  --   --    ethylene phosphonic acid    Maleic acid acrylic acid                      4.5    3.5    6.5  5.00 5.00    copolymer    Carezyme T-granulate                      0.15   0.20   0.40 0.3  0.25    Alcalase T-granulate                      0.60   0.80   0.80 0.50 0.30    Lipolase T-granulate                      0.35   0.25   0.35 0.3  0.20    Termamyl T-granulate                      --     --     --   --   0.3    Sodium silicate   2.00   --     --   2.00 2.0    Sodium sulphate   4.5    2.0    2.0  3.50 3.50    Percarbonate      --     --     --   --   --    Perborate         --     --     --   --   --    TAED              --     --     --   --   --    Polyvinylpyrrolidone                      0.1-1  0.1-1  0.1-1                                         0.1-1                                              0.1-1    Clay              --     12.0   --   --   --    Encapsulated perfumes                      0.2    --     --   --   0.2    Perfume           0.3    0.2    0.2  0.2  0.3    Minors            up to 100    ______________________________________

EXAMPLE II (F/G/H/I)

A compact granular detergent composition according to the presentinvention is prepared, having the following formulation:

    ______________________________________    % by weight of the total detergent composition                   F     G       H       I    ______________________________________    Polyhydroxy fatty acid amide                     10      --      --    --    Alkyl alkoxylated sulfate                     --      9       9     9    Alkyl sulphate   4.80    4.80    4.80  4.80    C.sub.45 alcohol 7 times ethoxylate                     4.00    4.00    4.00  4.00    Tallow alcohol 11 times                     1.8     1.80    1.8   1.8    ethoxylated    Dispersant       0.07    0.07    0.07  0.07    Silicone fluid   0.80    0.80    0.80  0.80    Trisodium citrate                     14.00   14.00   14.00 14.00    Citric acid      3.00    3.00    3.00  3.00    Zeolite          25.00   20.00   20.00 32.50    Diethylenetriamine pentan-                     0.6     0.6     0.6   0.6    ethylene phosphonic acid    Maleic acid acrylic acid                     5.00    5.00    5.00  5.00    copolymer    Carezyme T-granulate                     0.2     0.5     0.15  0.3    Alcalase T-granulate                     0.60    0.60    0.20  0.50    Lipolase T-granulate                     0.20    0.10    0.25  0.40    Termamyl T-granulate                     0.3     0.3     0.3   0.3    Sodium silicate  2.00    2.00    2.00  2.00    Sodium sulphate  3.50    3.50    3.50  3.50    Percarbonate     --      --      20    --    Perborate        15      15      --    --    TAED             --      5       5     --    Polyvinylpyrrolidone                     0.1-1   0.1-1   0.1-1 0.1-1    Encapsulated perfume                     0.2     --      --    --    Perfume          0.3     0.2     0.3   0.2    Minors           up to 100    ______________________________________

EXAMPLE III (A/B/C/D/E)

A compact granular detergent composition according to the presentinvention is prepared, having the following formulation:

    ______________________________________    % by weight of the total detergent composition                  A    B       C      D     E    ______________________________________    Polyhydroxy fatty acid                    10     --      --   --    --    amide    Alkyl alkoxylated sulfate                    --     9       9    9     --    Tallow alkyl sulphate                    1.80   1.80    1.80 1.80  1.80    C.sub.45  alkyl sulphate                    3.00   3.00    3.00 3.00  14.40    C.sub.45  alcohol 7 times                    4.00   4.00    4.00 4.00  4.00    ethoxylated    Tallow alcohol 11 times                    1.80   1.80    1.80 1.80  1.80    ethoxylated    Dispersant      0.07   0.07    0.07 0.07  0.07    Silicone fluid  0.80   0.80    0.80 0.80  0.80    Trisodium citrate                    14.00  14.00   14.00                                        14.00 14.0    Citric acid     3.00   3.00    3.00 3.00  3.0    Zeolite         25     20.0    20.0 32.50 38.5    Diethylenetriamine pentan-                    0.6    0.6     0.6  0.6   1.0    ethylene phosphonic acid    Maleic acid acrylic acid                    5.00   5.00    5.00 5.00  5.00    copolymer    Carezyme T-granulate                    0.2    0.5     0.15 0.3   0.1    Alcalase T-granulate                    0.60   0.60    0.20 0.50  0.30    Lipolase T-granulate                    0.20   0.10    0.25 0.40  0.35    Termamyl T-granulate                    0.3    0.3     0.3  0.3   0.3    Polyvinylpyrrolidone                    0.1-1  0.1-1   0.1-1                                        0.1-1 0.1-1    Sodium silicate 2.00   2.00    2.00 2.00  2.0    Sodium sulphate 3.50   3.50    3.50 3.50  3.5    Percarbonate    --     --      20   --    --    Perborate       15     15      --   --    0.5    TAED            --     5       5    --    --    Metallo catalysts                    0.1    0.1     0.1  --    --    Peroxidase      --     --      --   0.1   0.1    Encapsulated perfume                    0.2    --      --   --    0.2    Perfume         0.3    0.2     0.2  0.3   0.3    Phenyl sulphonate                    --     --      --   0.1   0.1    Minors          up to 100    ______________________________________

The above compositions (Example I (A/B/C/D/E), Example II (F/G/H/I) andExample III (A/B/C/D/E) were very good at displaying excellent washingperformance with outstanding fabric and color-care performance oncolored fabrics and mixed loads of colored and white fabrics.

Similar results were obtained when, as a polymeric dye transferinhibiting agent, polyvinylpyrridine N-oxide, N-vinylpyrrolidoneN-imidazole, polyvinyloxazolidone or polyvinylimidazole was incorporatedin the detergent compositions of Ex. I/II/III.

What is claimed is:
 1. A compact granular detergent composition forcleaning woolen fabrics comprising, by weight:i) from 0.001% to 10%polymeric dye transfer inhibiting agent having a molecular weigh fromabout 2,500 to 400,000 and selected from the group consisting ofpolyvinylpyrrolidones; polyvinyloxazolidnes; polyvinylimidazoles, andmixtures thereof; ii) from 0.01% to 2% protease having an isoelectricpoint below 10; iii) from about 3% to about 65% surfactant whichcomprises an alkyl sulfate; and iv) from about 10% to about 80% of awater-soluble organic ingredient selected from the group consisting ofhomopolymeric polycarboxylic acids, salts of homopolymericpolycarboxylic acids, copolymeric polycarboxylic acids, salts ofcopolymeric polycarboxylic acids, and mixtures thereof wherein thepolycarboxylic acid comprises at least two carboxyl radicals separatedby not more than two carbon atoms; v) 10% to 80% of a zeolite builderand wherein said compact granular composition has a density from 550 to950 grams/liter and wherein said composition has comprises no more than15% filler salt and wherein said composition is free of alkyl benzenesulfonates.
 2. A granular detergent composition according to claim 1wherein the protease shows a positive immunological cross-reaction withthe antibody of a protease selected from the group consisting ofproteases represented by the genus Subtilisin Carlsberg and proteasesrepresented by the genus Subtilisin BPN'.
 3. A granular detergentcomposition according to claim 1 wherein the polymeric dye transferinhibiting agent is selected from the group consisting ofpolyvinyloxazolidones, polyvinylimidazoles and mixtures thereof.